Unsaturated acid esters of oxy



Patented Jan. 8, 1952 UNS'ATURATED ACID ESTERS OF OXY- ALKYLATEDPHENOL-ALDEHYDE RESIN S Melvin De Groote, University City, and BernhardKeiser,,We.bster Groves, Mo., assignors to Petrolite Corporation, Ltd.,Wilmington, Del., a corporation of Delaware No Drawing. Application May6, 1949,

Serial No. 91,883

8 Claims. 1

The present invention is concerned with certain new chemical products,compounds or com positions which have useful application in variousarts. This application is a continuation-inpart of our co-pendingapplication Serial No. 64,469, filed December 8, 1948. It includesmeth-- ods or procedures for manufacturing said new chemical products,compounds or compositions themselves. Said new compositions are estersin 2 1 that at least 2 moles of alkylene oxide be introduced for eachphenolic nucleus.

Although the herein described products have a number of industrialapplications, they are of particular value for resolving petroleum emulsionsof the water-in-oil type, that are commonly referred to as cut oil,roily oil, emulsified oil," etc., and which comprise fine droplets ofnaturally-occurring waters or brines dispersed in which the acyl radicalis that of an unsaturated a more or less permanent state throughout theresinophore monocarboxy acid having less than oil which constitutes thecontinuous phase of the 8 carbon atoms, and the alcoholic radical isthat emulsion. This specific application is" described of certainhydrophile polyhydric synthetic prodand claimed in our co-pendingapplication Serial ucts; said hydrophile synthetic products being No.91,882, filed May 6, 1949, now Patent 2,542,009, oxyalkylation productsof 3 granted February 20, 1951. see also our co-pend- (A) An alpha-betaalkylene oxide having not ing application Serial No. 64,468, filedDecember more than 4 carbon atoms and selected from the 10, 1948, andnow abandoned. class consisting of ethylene oxide, propylene ox- The newproducts are useful as wetting, deteride, buty-lene oxide, glycide, andmethylglycide; gent and leveling agents in the laundry, textile and gand dyeing industries; as wetting agents and (B) Anoxyalkylation-susceptible, fusible, ordetergents in the acid washing ofbuilding stone ganic solvent-soluble, water-insoluble, phenoland brick;as wetting agents and spreaders in the aldehyde resin; said resin beingderived by reacapplication of asphalt in road building and the tionbetween a difunctional monohydric phenol like; as a flotation reagent inthe flotation sepand an aldehyde having not over 8 carbon atoms arationof various aqueous suspensions containand reactive toward said phenol;said resin being ing negatively charged particles such as sewage, formedin the substantial absence of trifunccoal washing waste water, andvarious trade tional phenols; said phenol being of the formula: wastesand the like; as germicides, insecticides, emulsifying agents, as, forexample, for cosmetics, OH 40 spray oils, water-repellent textilefinishes; as

lubricants, etc. R The oxyalkylated resins, used to provide thealcoholic radical of the new esters, are described in our Patent2,499,370, granted March '7, 1950, in which R is a hydrocarbon radicalhaving at and 2,542,009, granted February 20, 1951, and refleast 4 andnot more than 12 carbon atoms and erence is made to these patents for adescription substituted in the 2,4,6 position; said oxyalkylofphenol-aldehyde resins to produce the alcoated resin being characterizedby the introducholic products. For specific examples of the tion intothe resin molecule of a plurality of resinsreference is made to Examples10. through divalent radicals having the formula (R1O)11,, in 103a ofPatent 2,499,370. For examples of oxywhich R1 is a member selected fromthe class alkylated products derived from these resins, consisting ofethylene radicals, propylene radireference is made to the tables incolumns 31 cals, butylene radicals, hydroxypropylene radithrcugh 46 ofPatent 2,54 ,009. cals, and hydroxybutyle'ne radicals, and n is a Theacids herein employed to form the esters numeral varying from 1 to 20;with the proviso are unsaturated resinophores having less than 8 carbonatoms and exemplified by acrylic acid, methacrylic acid, ethacrylicacid, crotonic acid. etc.

Having obtained an oxyalkylated resin of the kind described we convertsuch polyhydroxylated compound into a total or partial ester of anunsaturated monocarboxy acid of the kind herein specified. One need notuse the acid as such, but can use any other obvious equivalent, such asthe acylchloride. the anhydride. ester, etc. Actually, due to the easewith which these acids polymerize, it is more desirable to use the acidas such. or the ester of a low molal alcohol. such as the ester ofmethyl alcohol or ethyl alcohol. Using such ester as the source of thedesired acidic radical, one need only employ the conventionalalcoholysis reaction so as to form the desired derivative. In suchreaction the low molal alcohol. i. e., methyl alcohol or ethyl alcohol,is eliminated. Our preference is to use the ethyl or methyl ester ofacrylic acid or methacrylic acid, or to use crotonic acid.

Example In the preparation of the esters the oxyalkylatedphenol-aldehyde resin, such as Exam le 1041) of Patent 2.542.009. isemployed. The euuipment used is substantially the same as describedunder Example 1a of Patent 2,499,370. It consists termined bycalculation from the hydroxyl value,

or it can be estimated from the probable structure of the product basedon the initial raw materials. In the procedure described, approximately250 to 325 grams of the xylene-containing solution described underheadings Examples of Patent 2,499,370, were employed, along with 200grams of added xylene. To this mixture was added the selected acid inthe stipulated amount, along with approximately 5% of para-toluenesulfonic acid as a catalyst. The mixture, including both reactants. theadded xylene and a catalyst, was heated and stirred until the refluxingaction started. Refluxing was continued until the theoretical amount ofwater had been collected in the trap, or until the evolution of waterceased. More than theoretical amount of water may be found in the trap,since the chemicals obtained contain a small amount of water as animpurity.

As a specific example, 322.6 grams of the xylenecontaining oxyalkylatedresin, Example 11117 of Patent 2,542,009, are reacted with enoughcrotonic acid to neutralize one-fourth of the hydroxyl groups in theresin. In this case 7.1 grams of acid were employed. There was addedalso to the flask 200'grams of added xylene and grams of paratoluenesuifonic acid as a catalyst. The mixture was heated at 140 C. for 3hours, until 4.1 ml. of

water were evolved.

Example 20 The same procedure was used as in Example 10.

preceding, except that enough acid was used to neutralize one-half ofthe hydroxyl groups of the resin.

As a specific example, 210 grams of the xylenecontaining resin 1161) ofPatent 2,542,009 were reacted with 13.8 grams of crotonic acid in thepresence of 200 grams of additional xylene and 20 grams of para-toluenesulfonic acid at 140 0., until 9.2 grams of water were evolved. Thistook 4.5 hours.

Example The same procedure was used as in Example 10. preceding, exceptthat enough acid was used to neutralize three-quarters of the hydroxylgroups of the resin.

As a specific example, 240.3 grams of the xylenecontaining resin 1261)of Patent 2,542,009 were reacted with 25.6 grams of crotonic acid in thepresence of 200 grams of additional xylene and 20 grams of para-toluenesulfonic acid as a catalyst. Reflux was at 141 C. for 5 hours. 15.1 ml.of water were evolved.

Example The same procedure was used as in Example 1e, preceding, exceptthat enough acid was used to neutralize all of the hydroxyl groups ofthe resin. As a specific example, 252.6 grams of the xylenecontainingresin 10'?!) of Patent 2,542, were reacted with 25.9 grams of crotonicacid in the presence of 200 grams of additional xylene and 20 grams ofpara-toluene sulfonic acid as a catalyst. Reflux was at 144 C. for 6hours. 7.6 ml. of water were evolved.

Example 5c The same procedure was used as in Examples 10 to 40,preceding, except that instead of using crotonic acid, methacrylic acidwas used.

As a specific example 283 grams of the xylenecontaining resin 1071) ofPatent 2,542,009 were reacted with 28.9 grams of methacrylic acid in thepresence of 200 grams of additional xylene and 20 grams of para-toluenesulfonic acid as a catalyst. The mixture was refluxed at 144 C. for 3hours until 8.0 ml. of water were evolved.

Example If desired, the reaction can be carried out also bytrans-esterification. That is, the xylene-containing oxyalkylatedphenol-aldehyde can be heated with an ester of an unsaturated acid inthe presence of sodium methylate or para-toluene sulfonic acid as acatalyst until the corresponding alcohol is driven ofi. As a specificexample, grams of resin Example 10Gb of Patent 2,542,009 were reactedwith 816 grams of methylacrylate in the presence of 0.6 gram of sodiummethylate at 108 C. for 5 hours. 3 ml. of methyl alcohol were drivenofl.

Example 7c f The same procedure was followed as outlined in Example 60,preceding.

As a specific example, -75 grams of resin 125b of Patent 2,542,009 werereacted with 8.6 grams of methyl acrylate in the presence of 0.6 gram ofsodium methylate for one-fourth of an hour at 40 C. 1.1 ml. of methylalcohol was obtained.

Example The same procedure was followed as outlined in Example 60,preceding.

As a specific example, 0.6 gram of para-toluen sulfonic acid was used,instead of the sodium methylate, as outlined in Example 70, preceding.The reaction was continued for 4 hours at 138 C. 3.2 ml. of methylalcohol were obtained.

A number of additional examples; are summarized in the following table:In all cases, 200

grams of additional xylene were used and grams of para-toluene sulfonicacid were used as a catalyst.

oxyalkylation products of (A) an alpha-beta alkylene oxide having notmore than fem-130111 atoms and selected from the class consisting of areon a

Xylene Water ing Resin Grams Weight, Time, Temp,

Ex. No used 3532: Acid Grams Hours C. ggfi 322. 6 77. 4 28.4 5. 5. 141'8.7 237. 5 62. 5 22.8 6.0 r 139 9.5 210. O 89. 2 27. 6 4. 0 140 2. 0240. 3 .59. 7 34. 2 5. 75 141 4.6 254. 6 45.4 19.8 2.5 I 143 5.0 255. 344. 7 l9; 0 6. 5 i 143 7. 5 250. 0 50. 0 23. 9 4. 142 6.4 268.0 32. 020. 5 51 0 I44 6. 5 233.0 67.0 22. 7' 6. 5 143 4.3 262. 2 37. 8 21. 5 6.0 1.41 8. 2 254. 8 45. 2 1-9; 2 4'. 25 143 6. 3 253. 8 46. 2 26; 7- 3.75 143 5 7. 5 262. 2 37. 8 21. 5 3. 75 142 8. 2 262. (l 38. 0 21.5 3. 5140 I S. 0 264. 0 67. 0 22. 7 3. 0 144 7. 0, 228. 7 71.3 1216 2. 0 1404.1 24& 4 51. 6 30. O 2. 25 1'45 9L0 Having thus described our.invention, what we claim as new and desire to secure by Letters Patentis:

1. An ester in which the acyl radical is that of an unsubstitutedalpha-beta mono-olefinic monocarboxy acid saturated except for thealpha-beta olefinic linkage and having less than 8 carbon atoms, and thealcoholic radical is that of certain hydrophile polyhydric syntheticprod ucts; said hydrophile synthetic products being oxyalkylationproducts of (A) an alpha-beta alkylene oxide having not more than 4carbon atoms and selected from the class consisting of ethylene oxide,propylene oxide, butylene oxide, glycide, and methylglycide; and (B) anoxyalkylation-susceptible, fusible, organic solventsoluble,water-insoluble, phenol-aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and having one functional group reactive towardsaid phenol; said resin being formed in the substantial absence ofphenols of functionality greater than 2; said phenol being of theformula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (13.10), in which R1 is a member selectedfrom the class consisting of ethylene radicals, propylene radicals,butylene radicals, hydroxypropylene radicals, and hydroxybutyleneradicals, and n is a numeral varying from 1 to 20; with the proviso thatat least 2 moles of alkylene oxide be introduced for each phenolicnucleus.

2. An ester in which the acyl radical is that of an unsubstitutedalpha-beta mono-olefinic monocarboxy acid saturated except for thealpha-beta olefinic linkage and having less than 8 carbon atoms and thealcoholic radical is that of certain hydrophile polyhydric syntheticproducts; said hydrophile synthetic products being in which R is ahydrocarbon radical having at least 4 and not more than 12 carbon atomsand substituted in one of the positions ortho and para; saidoxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (R10)n, in which R1 is a member selectedfrom the class consisting of ethylene radicals, propylene radicals,butylene radicals, hydroxypropylene radicals, and hydroxbutyleneradicals, and n is a numeral varying from 1 to 20; with the proviso thatat least 2 moles of alkylene oxide be introduced for each phenolicnucleus; and with the final proviso that the hydrophile properties ofthe ester as well as the oxyalkylated resin in an equal weight of xyleneare suflicient to produce an emulsion when said xylene solution isshaken vigorously with one to three volumes of water.

3. An ester in which the acyl radical is that of an unsubstitutedalpha-beta mono-olefinic monocarboxy acid saturated except for thealphabeta olefinic linkage and having less than 8 carbon atoms, and thealcoholic radical is that of certain hydrophile polyhydric syntheticproducts; said hydrophile synthetic products being oxyethylationproducts of (A) ethylene oxide; and (B) an oxyethylation-susceptible,fusible, organic solvent-soluble, water-insoluble phenolaldehyde resin;said resin being derived by reaction between a difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and having onefunctional group reactive toward said phenol; said resin being formed inthe in which R is a hydrocarbon radical having at least 4 and not morethan 12 carbon atoms and substituted in one of the positions ortho andpara; said oxyethylated resin being characterized by the introductioninto the resin molecule at the phenolic hydroxyls of a plurality ofdivalent radicals having the formula (CzHqOMj wherein n is a numeralvarying from 1 to 20; with the proviso that at least 2 moles of ethyleneoxide be introduced for each phenolic nucleus; and with the finalproviso that the hydrophile properties of the ester as well as theoxyethylated resin in an equal weight of xylene are sufiicient toproduce an emulsion when said xylene solution is shaken vigorously withone to three volumes of water.

4. An ester in which the acyl radical is that of an unsubstitutedalpha-beta mono-olefinic monocarboxy acid saturated except for thealpha-beta olefinic linkage and having less than 8 carbon atoms and thealcoholic radical is that of certain hydrophile polyhydric syntheticproducts; said hydrophile synthetic products being oxyethylationproducts of (A) ethylene oxide; and (B) an oxyethylation-susceptible,fusible, organic solvent-soluble, .water-insoluble, lowstagephenol-aldehyde resin having an average molecular weight correspondingto at least 3 and not over 7 phenolic nuclei per resin molecule; saidresin being derived by reaction between a difunctional monohydric phenoland formaldehyde; said resin being formed in the substantial absence ofphenols of functionality greater than 2; said phenol being of theformula:

in which R is an aliphatic hydrocarbon radical having at least 4 and notmore than 12 carbon atomsand substituted in oneof the positions orthoand para; said oxyethylated resin being characterized by theintroduction into the resin molecule at the phenolic hydroxyls of aplurality of divalent radicals having the formula (C2H40)n; wherein n isa numeral varying from 1 to 20; with the proviso that at least 2 molesof ethylene oxide be introduced for each phenolic nucleus; and with thefinal proviso that the hydrophile properties of the ester as well as theoxyethyated resin in an-equal weight of xylene are sufficient to producean emulsion when said xylene solution is shaken vigorously with one tothree volumes of water.

5. The product of claim 4, wherein R is substituted in the paraposition.

6. The product of claim 4, wherein R is a butyl radical substituted inthe para position. 7. The product of claim 4, wherein R is an amylradical substituted in the para position.

8. The product of claim 4, wherein R is a nonyl radical substituted inthe para position. MELVIN DE GROOTE.

BERNHARD KEISER.

REFERENCES CITED The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 2,178,829 Bruson et al Nov. 7,1939 2,499,365 De Groote Mar. 7, 1950

1. AN ESTER IN WHICH THE ACYL RADICAL IS THAT OF AN UNSUBSTITUTEDALPHA-BETA MONO-OLEFINIC MONOCARBOXY ACID SATURATED EXCEPT FOR THEALPHA-BETA OLEFINIC LINKAGE AND HAVING LESS THAN 8 CARBON ATOMS, AND THEALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETICPRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEING OXYALKYLATIONPRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE,PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, AND METHYLGLYCIDE; AND (B) ANDOXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENTSOLUBLE,WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN; SAID RESIN BEING DERIVED BYREACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVINGNOT OVER 8 CARBON ATOMS AND HAVING ENE FUNCTIONAL GROUP REACTIVE TOWARDSAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OFPHENOLS OF FUNCTIONALITY GREATER THAN 2; SAID PHENOL BEING OF THEFORMULA: